Process and products of sulfurization of linear methylpentadiene polymers



Patented Sept. 6, 1949 PROCESS AND PRODUCTS or soLFUinzA- TION F LINEAR METHYLPENTADI'ENE POLYMERS Rupert 0. Morris, Berkeley, and Jane-"L. Winkle, San Lorenzo, Calif; as rgnorsto" Development Compan a corporation of Dela y, San" Frenoisoo; C'a'lifi, ware No Drawing. Application Septeinbrlli, 1946; Serial No. 697,376

8 Claims.

This invention relates to' a process for the sulfurization of lowmolebular weight linear polymers of the m'ethylpentadienes and to the products' thereof.

Processes for the sulfurization of hydrocarbon polymers have been known for some time. Such processes, however, are directed to the sulfurizationof high molecular'weight cyclic polymers and when'theyare' used'to sulfurize 10w molecular weight polymers little if any sulfurization occurs. Even when the conditions of the known processes are varied, such as elevating the temperature; the sulfuriza'tion of low molecular weight polymers (e. g. tetrameric isobutylene) cannotbe accomplished without rapid degradation of the polymer.

It has been discovered, however, that members of a particular group'of the low molecular weight polymers, 1. e. the low molecular weight linear polymers of the methylpentadiene's, act 'diiierently from the other low molecular Weight polymers and have an inherent property within their structure that enables themto' be sulfurized at the elevated temperatures without the expected degradation of the polymer; It has also been found that the resulting sulfurized polymers of the methylpentadienes have unique properties which enable'them to be used for a great many beneficial purposes more fully described hereinafter.

It is an object of the present invention, therefore, to provide a method for the sulfurization of low molecular weight linear polymers of methylpentadi'en'es. It is a further object of the invention to provide a new"class of materials which possesses ma'ny advantageous properties making the products useful in a great many industrial applications; other objects and advantages of the invention will be apparent from the following detailed description thereof.

Molecular weights'of polymers of the type coming within the'scope of the present invention are usually" describedin comparison" to the molecular weight of natural rubber. Rubber-like polymers having a molecular weight in the'vicinity of the molecular weight of 'natural rubber, i. e. around 50,000 to 300,000, are termed high molecular weight polymers. Polymers having a molecular weight in the'vicinity of 101000 01 l'e'ss aretermed lowmolecula-r weightpoly'mers; Bythe term low molecular-weight polymer, asemployed through out the specificationand appended'claims; is meant'those polymershavinga molecular weight of approximately -5 ,0'0'0*or less."

By the term1inear polymer? as employed I preferred methodthroughout the splficaiti and appended claims; is meent trios' poryrners ossessing a structure wh'reiiifthe"moledules':of the reactant or'reacta'nts afejoiiied together inano'pen-ohai'n type structure. sue umea w polymers are readily distinguished 'ffoiffth closed; cyclic structures of other partners means of infra-red analysis; I I

The methyli er'itadienes'fw'th' which the invention is concerned are bra j-"chain 1,3- he'x adienes" having a streaman n of 5 carbon atoms, specifica l 2-riietfi I-i's pentmiijene, 3- methyr-'1,3j-pentadi e)" 4-mt1'ly 1- L3-pe1itadiefie.

The" bove-described ow molecular weight linear polymers of the mthylpentadienes which are sllIfii'ri'zdin' 'ac'cbfdance with the invention may be produced, by any suitablemethod. They may be produced, forexample', by subjecting the methylpentadienes to an elevated temperature in a sealed tube for an eiit'endedperiod of time. They alsom'ay be "p'rodu'o'ed by treating the monomer with a concentratedacid such-as sulfuric acid, or by subjecting the methylpe'ntadienes to the action of e polymerizing catalyst. The more is a variation or the procedure described 7 in' the ec-pending application Serial No. 534,342', filed 5 ,;-l 94 4, for the production of high molecular weight linear polymers of the methylpentadienes' By this; preferred method the polymerization is accomplished by dissolving the methylpentadieneor methylpentadienes in a diluent and then treating the resulting solution with a Friedel-Craf-ts-type catalyst at an elevated temperature, v V

In the productiomof thepolymers by'the preferred method, any of the above-described meth ylpentadienesmay be emp1oyed.-- A'sing'le methylpentadiene-ean be -polymerizedi-alone or two or more 'methy-lpentadienesecan A be polymerized in admixture- -with' one anothen It is preferred to employ a mixture of 2-inethyl-1,3-pentadiene and i -methyl -lfimentadiene, eygsamixture of about 8 5'% oi; Z-methyklB-pentadienewith about 15% of 4- me th yl-l,3 -pentadiene, such as may be producedfby the dehydration of 2-methyl-2, i'-pentanediol. In general, polymerization inhibitors such as tertfbutyl catechol' and others, which may be present in the monomer, need not be removed; The polymerization --occurs in ac corda'i'ice" with the prelferredmethod inthe presence of such inhibitors.

Any inert diluent, with the; exception of the olefin'ic ma ten-s es w be used to dissolve the methylpenftadieiis the preferred method or 'poiymenzeoon, The "olfini'" hydrocarbons are undesirable as they tend to form complexes with the metallic halide catalysts or cause the formation of polymers having a much higher molecular weight than that desired in the present process. Preferred diluents are liquids which are solvents for both monomer and polymer under the conditions involved. The paraflin hydrocarbons are particularly useful as diluents for the polymerization process. Examples of suitable solvents are ethane, propane, the butanes, the pentanes, octane, methyl chloride, ethyl chloride and propyl chloride, and mixtures thereof. Aromatic compounds should usually be avoided because of the danger of alkylation thereof.

The amount of the catalyst to be used in the polymerization reaction will depend upon the particular catalyst and diluent being added to the reaction and the particular methylpentadiene or mixtures of methylpentadienes being polymerized. In all cases, however, the reaction goes 3;

almost to completion with the addition of only a 'very small amount of catalyst. In general, amounts as small as about 0.2 part of catalyst per 100 parts of the methylpentadienes are satisfactory, although where traces of moisture are present in the reaction mixture somewhat larger amounts, e. g. 0.75 part of catalyst per 100 parts of the methylpentadienes, may be required. The rate of polymerization and the conversion of the monomer to polymer increases with increasing amounts of catalyst, at least up to about 4 parts of catalyst per 100 parts of the methylpentadienes, beyond which an increase in catalyst may not appreciably increase the rate of polymerization. Amounts as large and larger than 5 parts :3

of catalyst per 100 parts of the methylpentadienes have been used.

For the production of the desired low molecular weight linear polymers the polymerization process should be conducted at temperatures above 0 C. The upper limit for the temperature range of the polymerization should not be substantially above 100 C. The addition of the Friedel-Crafts catalyst to the methylpentadiene solution results in an exothermic reaction which usually furnishes sufi'lcient heat to carry the polymerization to completion without the addition of any external heat. External heat may be applied when desired or necessary but in some cases, however, cooling of the reaction mixture may be necessary. The exact temperature in each case depends upon the particular reactants and especially upon the type of diluent used. The polymerization reactions carried on in a pentane solution, for example, proceed at around C. while those reactions carried on in an octane solution proceed at around 100 C.

The polymerization is preferably carried out in the liquid phase under atmospheric pressures. However, subatmospheric or superatmospheric pressures may be employed if desired or necessary.

The ratio of the diluent to the methylpentadienes may be varied over a wide range. Amounts as small as about 10 parts of diluent per 100 parts of the methylpentadienes are elfective. Mixtures within the range of about '70 parts to about 500 parts of diluent per 100 parts of the methylpentadienes are preferred. Much higher ratios, e. g. as high as 1,000 parts of diluent per 100 parts of the methylpentadienes can be employed.

Substantially any Friedel-Crafts catalyst may be employed which is soluble in the methylpentadienes or which can be added as a solution in an inert solvent which is also a solvent for the methylpentadienes. By the term Friedel-Crafts catalyst is meant any catalyst capable of being used for the Friedel-Crafts type condensation. Examples of Friedel-Crafts catalyst are hydroiyzable metallic halides such as stannic chloride, aluminum chloride, zinc chloride, ferric chloride, titanium tetrachloride, antimony pentachloride, and boron trifluoride. The catalyst should usual- 1y be in substantially anhydrous condition and is preferably of a high degree of purity.

To promote a smoother reaction it is sometimes preferred to dissolve the catalyst in an inert liquid before adding it to the reaction mixture. When the catalyst is added without a solvent immediate local polymerization may occur in the region about the added catalyst, preventing the uniform admixture of the catalyst with the methylpentadiene and resulting in an inhomogeneous product. Methyl chloride, ethyl chloride and ZA-dimethyl-sulfolane are solvents which may be used to dissolve the catalyst. The boron trifluoride is particularly more active as a catalyst for the polymerization of the methylpentadienes when it is dissolved in ethyl ether with which it forms an active boron fluorideethyl ether complex. The ethyl chloride solutions of aluminum chloride and stannic chloride and the boron trifluoride-ethyl ether complex are the more preferred catalysts for the polymerization of the methylpentadienes.

The polymerization may be carried out in any suitable vessel which permits the addition of the catalyst and the stirring and refluxing of the reactants. In some cases it may be advisable to spray the catalytic solution over the methylpentadiene mixture, instead of adding it portionwise, in order to induce a smoother reaction. The reaction mixture may be blanketed with air, nitrogen, carbon dioxide or other fluid, as desired. The polymerization may be carried out in a continuous or batchwise manner.

The time required for the reaction is dependent upon many factors including the nature and the properties of the ingredients of the reaction mixture, the conditions under which the reaction is conducted and the degree of completion desired. In the higher temperature range and with substantial amounts of catalyst a conversion of monomer to polymer may be obtained in 2 hours. Under other conditions 24 hours or more may be required to obtain a high percentage of conversion.

Upon completion of the reaction the polymer is separated from the reaction mixture, which will generally include the catalyst, diluent and a small amount of the unreacted methylpentadiene by any suitable means comprising such steps as, for example, solvent extraction, washing, filtration and the like.

The products resulting from the hereinabovedescribed polymerization process are thick, oily linear polymers having a molecular weight from about 400 to about 5,000. The specific molecular weight of the polymers depends upon the particular diluent and particular catalyst used in the polymerization process. The use of the boron trifluoride-ethyl ether complex with isopentane as the solvent, for example, gives light colored thick oils with a molecular weight of about 720. When aluminum trichloride is used with isopentane as the solvent the polymer is a clear, thick, oily material with a molecular weight of about 1720. Higher or lower molecular weights than the above described may be obtained by merely varying the reactants. Polymers having a molecular weight -of --about "-492 oan be should V v 1 as 0.5% by weight may be employed. 'Thepreobtained, for-example, -bysusing the borontrifluorideethyl other com- -plex with an --isopentane solution of a methylpentadiene that had -not beenpreviously =flash distilledf-rom a %-sodium hydroxide solu- -tion. The-usepf aluminum trichloride with a butane solution -in the polymerization reaction produces methylpentadiene -=polymers having a molecular weight 'ashigh-:asl 3,000.

Infra-red 'ray analysisof the low molecular weight polymers of methyl 'pentadienes indicates that the polymers havea linear type structure.

Iodine determinations indicate that the polymers also possess 'a doub le-bond tad'iene molecule within thestructure. The polyfor :each methylpenmers are thus probably products of principally lA-polymerization,1,2-polymerization. Substantially no 1,3polyi'nerization" occurs. In accordance with the above-analysis the: polymer resulting from the-addition of theboron-trifluorideethyl ether complex to a mixture :of Z-methyl- 1,3-pentadieneand 4-methyl-1,3-pentadiene "dissolved inisopentane may be described'as a light colored oil having-the structure of 9 units of the -methylpentadienes joinedin a linear typestructure-and possessing one-double bond permethylpen-tadiene molecule.

Molecular weight --deter-minations 'referred to in this application were made-inaccordance with the. procedure described -by J. *Nair'in the Bureau of-Standardsdournal-of Research 14..

The sulfurization of the-(low V molecularweight linearpolymersof the methylpentadienes' may be effected in anysuitable manner. 1 The process consists essentially in the reaction of-su-lfurwith -the polymers -at an elevated temperature to give products containing chemically combined sulfur. The products appear to-be definite =compounds,

although the natureof the reaction involved and the exact -iden-tityof -the compounds formedare not entirely understood.

The amount of the sulfur to be combined with the methylpentadienepolymers will vary up to approximately 25% by weight of the combined of the process of the invention and, therefore,

be avoided. Amounts'ofsulfur as small ferred amountof sulfur" tobe"c'ombined with the polymer will vary between about 5% and "by weight of the combined amount of sulfur-and themethylpentadiene polymer being sulfurized.

The desired total'amount'of'sulfur may be ""addedall at'once or portions may be added at intervals. The sulfur may be added before or after the methylpentadielne polymer has been brought to the desired temperature. After the sulfurhas' been added to the polymer'the mixture be then maintained,' preferably with stirring or "other 'merhoesoragitation, undertherequired conditions of he'at'and pressure.

Slow sulfurization begins at temperatures as low as about-150"- "C. L'Temperatures within the range of 'from' about I60 Cf toabout 200C. may

be employed under practical conditions. The more narrow range offrom 160C: to about 170 Cfis' preferred. F'Wh'en the reaction is carriedout in accordance" with the "invention, noappreciable "amount of hydrogen" "sulfide is evolved.

The sulfurization is 'preferably'carried out in the liquid phase or atleast undersuchconditioris blanket of an oxygen-free fluidsuchaspxygenfree nitrogen, carbon dioxide, etc. The'sulfurization reaction may be carried out in a continuous or discontinuous manner. -It may be efl'ectedvin the presence or absence of a homogenizingisubstance, preferably a substance -which fs-nonreactive and liquid under the-reaction conditions employed and which is asolvent-for----boththe sulfur and the methylpentadienepolymers. If desired, sulfurization may be carried out on the methylpentadiene polymer in situ in its intended use. For example, where the sulfurized polymer is to be employed as a hydrocarbon lubricating oil additive, the unsulfurized polymer may-befirst dissolved'in the oil and there subjected :to sulfurization in accordance-with the invention.

The duration of the sulfurizationtreatment is dependent principally upon the relativei proportions of polymer andsulfuremployed'thereaction conditions including the particular-temperatures and pressures involved, and the degreeof-sulfurization desired. Satisfactory productsmay be'produced in some cases even after 1or 2. hours t1-'eatment. In other cases the treatment requires"! or 5 hours. Improved products'having greater stability and homogeneity may be obtained by heating in accordance with the invention .for'from about 10 toabout 30 hours.

Following sulfurization the productsmay be separated from any other remaining-ingredients of the reaction mixture and further'purified in any suitable known or special manner. -Inert 'diluents, if present, may be-removedby distillation, by solvent extraction, or thelike. :Excesses of sulfur may separate out on: cooling. of the reaction mixture and maybe removed therefrom by-filtration or the like. Remaining 'sulfur may be separated'by taking up the product in asuitable solvent, such as an aliphatic hydrocarbon, e. g. isopentane, isooctane; etc.;-or other suitable solvents, followed by recovery :in-thewusual-manner. However, where not more than about-15% of sulfur based on the combined amount of sulfur and methylpentadiene polymer has been added and the mi'xturehas" been treated for"5"ho'urs or" more, all of the added'sulfur will'ordinarily have reacted and no purification "orrecovery 'procedures need be takemprovided 'inertdiluents','etc. are not present.

The products of sulfurization' "in accordance with the process of the inventioncon sist"essen- 60 tially of low molecular weight""linear polymers of the methylpentadiene, which polymers contain chemically combined sulfur. Polymers "of improved properties can be produced which contain "only a very small amount, e. g. about'0.5"%, of

combined sulfur. Preferredpolymers"contain from about 5% to about 15% of combined sulfur 'based on the combined amount of sulfur and methylpentadiene polymer. Other polymers" in accordance with the invention containing up to 25% or even somewhatmore "combined sulfur, while useful formany. purposes, are or. reduced "general value becauseth'ey may tend to lose=sulfur 'at elevated temperatures.

' The niethylpentadiene 1 polymers 3 containing amounts 'oisuifur up to about 15% -ofcombined sulfur are particularly valuable as additives for lubricating oils to be used at elevated temperatures as the sulfur is firmly held within the polymer and will not be liberated at the high temperatures to corrode the lubricated parts.

-The preferred sulfurized polymers as well as the other sulfurized products coming within the scope of the invention are valuable ingredients in all kinds of vulcanizable compositions. They are particularly valuable in rubber-like compositions, such as those containing natural rubber, reclaimed rubber, synthetic rubber, or mixtures of these with one another and with other substances. The sulfurized polymers act not only as plasticizers and tackifiers but also have been found to act as vulcanization accelerators, decreasing the time required for vulcanization. They also may be employed with synthetic rubber such as the rubbery polymers and copolymers of 1,3-butadiene. Compounds which may be ccpolymerized with these and other dienes include styrene, dichlorostyrene, alpha-methyl styrene, acrylonitrile, methacrylonitrile, methyl methacrylate, methyl vinyl ketone, etc. Representative are copolymers of 1,3-butadiene with styrene and of 1,3-butadiene with acrylonitrile. The sulfurized polymers are effective with many other synthetic elastomers.

In addition it has been found that these new sulfurized low molecular weight linear polymers of the methylpentadiene are effective plasticizers for synthetic resins and other plastics, such as casein and other protein plastics, lignin plastics, cellulose derivatives, synthetic linear polyamides, synthetic linear polyesters, phenol-aldehyde type resins, urea-aldehyde type resins, alkyd resins, resinous polymers of compounds having in the molecule one or more unsaturated carbon-tocarbon linkages, etc.

The sulfurized polymers have many other uses. They have vermicidal action and are efiective ingredients in vermifuges such as sheep dips. They may be employed in other biocides such as insect sprays, fungicides, etc. They may be employed as textile assistants, as ingredients in coating compositions, as components of cutting oils, and as chemical intermediates.

Some of the ways in which the invention can be carried out are illustrated by the following examples.

Example I 592 grams of methylpentadiene (approximately 85 parts by weight of 2-methyl-1,3-pentadiene and parts by weight of 4-methyl-L3-pentadiene) previously flash distilled from a 10% NaOH solution were dissolved in isobutane and placed in a flask fitted with a stirrer and a large reflux condenser. 4.5 grams of SnCh in ethyl chloride were then added to the methylpentadiene solution. The rate of addition of the catalyst was such that the heat of polymerization caused the solvent to reflux vigorously. After a period of 3 hours the reaction appeared to be complete and the reaction mixture was diluted with water and washed several times. The solvent was then removed and the polymer which was a cloudy, viscous mass was dried at 100 C. under reduced pressure.

grams of sulfur were added portionwise to 151 grams of the above-described low molecular weight linear polymer of methylpentadiene. In an atmosphere of nitrogen the mixture was heated to 160 C. to 175 C. for 18 hours. The re- ;action mixture was then taken up in isopentane and filtered to remove any uncombined sulfur clearly indicated that the sulfur was firmly combined in the polymer and that the sulfurized low molecular weight linear polymer could very effectively be used as an additive for lubricating oils.

Example II 570 grams of methylpentadiene (approximately parts by weight of Z-methyl-LS-pentadiene and 15 parts by weight of 4-methyl-L3-pentadiene) previously flash distilled from a 10% NaOH solution were dissolved in isopentane (2 liters of isopentane per liter of methylpentadiene) and placed in a flask fitted with a stirrer and a large reflux condenser. 0.5 gram of BF: in ethyl ether was then added to the methylpentadiene solution. The heat of polymerization resulting from the addition of the catalyst maintained the temperature at around 35 C. After a period of 2 hours the reaction appeared to be complete and the mixture was diluted with water and washed several times. After removal of the solvent 519 grams of a pale yellow, honey-like material was obtained. Infra-red ray analysis of the polymer revealed that it was a linear polymer and molecular weight determinations showed the molecular weight to be around 809.

The pale yellow, honey-like material is then heated with sulfur according to the procedure outlined in Example I to obtain the desired sulfurized polymer.

Example III In the manner described in Example I, 460 grams of a methylpentadiene previously flash distilled from a 10% NaOH solution were dissolved in isopentane and then treated with 4 grams of AlCls in ethyl chloride. After refluxing for an hour the mixture was washed several times and the solvent separated out. 40 grams of a light brown, oily material were obtained as the final product. Infra-red ray analysis revealed that the material was a linear polymer, and its molecular weight was found to be around 1760.

The light brown, Oily material is then heated with sulfur according to the procedure outlined in Example I to obtain the desired sulfurized polymer.

Example IV 572 grams of methylpentadiene that had not been previously flash distilled from a 10% NaOI-I solution were dissolved in isopentane and placed in a flask fitted with a stirrer and a reflux condenser, 1.25 grams of BF3 in ethyl ether were then added to the methylpentadiene solution. The heat of polymerization caused the solvent to reflux vigorously. After a period of 2 hours the reaction appeared to be complete and the reaction mixture was diluted with water and washed several times. After the solvent was removed a yield of 475 grams of a brown, viscous material was obtained. Infra-red ray analysis of the product revealed that it was a linear polymer and its molecular weight was determined as being around 590.

The polymer is then heated with sulfur according to the general procedure described above to obtain the desired sulfurized polymer.

We claim as our invention:

1. A sulfurized low molecular weight linear polymer of 2-methyl-1,3-pentadiene and 4- methyl-1,3-pentadiene.

2. A sulfurized liquid mixture of an unsaturated, low molecular weight linear polymer of 2- methyl-1,3-pentadiene and 4-methyl-1,3-pentadiene.

3. A sulfurized low molecular weight linear polymer of a member of the group consisting of 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyI-L3-pentadiene, and a mixture of at least two of the foregoing members.

4. A process comprising heating sulfur with a liquid mixture of unsaturated low molecular weight linear polymers of 2-methyl-1,3-pentadiene and 4-methyI-L3-pentadiene in a substantially inert atmosphere at a temperature between 160 C. and 170 C.

5. A process comprising heating sulfur with a low molecular weight linear polymer of Z-methyl- 1,3-pentadiene and 4-methyI-L3-pentadiene in a substantially inert atmosphere at a temperature between 160 C. and 200 C.

6. A process comprising heating sulfur with a liquid unsaturated low molecular weight linear polymer of a member of the group consisting of 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-L3-pentadiene, and a mixture of at least two of the foregoing members, in a sub- 10 stantially inert atmosphere at a temperature between C. and C.

7. A process comprising heating sulfur with a low molecular weight linear polymer of a member of the group consisting of 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3- pentadiene, and a mixture of at least two of the foregoing members, in a substantially inert atmosphere, at a temperature between 160 C. and 200 C.

8. A process comprising heating sulfur with a low molecular weight linear polymer of a member of the group consisting of 2-methyl-1,3-pentadiene, 3-methyl-l,3-pentadiene, 4-methyl-1,3- pentadiene, and a mixture of at least two of the foregoing members, in a substantially inert atmosphere at a temperature below that at which any substantial amount of hydrogen sulfide is formed.

RUPERT C. MORRIS. JOHN L. VAN WINKLE.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,093,752 Duecker et a1. Sept. 21, 1937 2,225,573 Tendeloo Dec. 17, 1940 2,337,473 Knowles et a1 Dec. 21, 1943 2,338,829 Werntz Jan. 11, 1944 2,402,456 Signaigo June 18, 1946 2,422,275 Winning June 17, 1947 

